Hollow V2O5 spheres constructed from plate-like particles were synthesized. These materials exhibited a tremendous pseudocapacitance effect with a high capacitance of 479 Fg(-1) at 5 mVs(-1) when used as supercapacitor electrodes in a solution of 5 M LiNO3. After the surface of hollow V2O5 spheres was coated with PPy, the composite electrode was formed and its electrochemical properties were also improved. This composite material exhibited the capacitances of 559 Fg(-1) at 3 A g(-1) by GCD and 566 Fg(-1) at 5 mV s(-1) by CV, respectively. At the same time, the capacity retentions of 70% and 66% were respectively achieved even after 100 cycles. (C) 2013 Elsevier Ltd. All rights reserved.